Department of Chemistry , University of Richmond , Richmond , Virginia 23173 , United States.
Department of Chemistry , Vanderbilt University , Nashville , Tennessee 37235 , United States.
Inorg Chem. 2019 Dec 2;58(23):15983-15992. doi: 10.1021/acs.inorgchem.9b02467. Epub 2019 Nov 12.
A combined synthetic-theoretical study has been undertaken to determine the factors that influence transannulation in azaphosphatranes. The commonly used proazaphosphatrane P(-BuNCHCH)N and several of its oxidized congeners are used as model systems. The haloazaphosphatranes of P(-BuNCHCH)N were synthesized, including a rare fluoroazaphopshatrane, and used as references for computational investigations. Comparisons of the experimental and theoretical observations highlight the flexibility observed in transannulated atranes and the potential for multiple local energetic minima depending on the identity of the equatorial substituents for a given azaphosphatrane. Theoretical calculations also identify the role of the ethylene linker in azaphosphatrane bonding, the influence of transannulation on P-electrophile interactions, and the contribution of electrostatic interactions to transannulation.
已经进行了综合理论研究，以确定影响氮杂膦烷transannulation 的因素。常用的前氮杂膦烷 P(-BuNCHCH)N 和其几种氧化同系物被用作模型体系。合成了 P(-BuNCHCH)N 的卤代氮杂膦烷，包括一种罕见的氟氮杂膦烷，并用作计算研究的参考。实验和理论观察结果的比较突出了 transannulated atranes 中观察到的灵活性，以及取决于给定氮杂膦烷的赤道取代基的身份，存在多个局部能量极小值的可能性。理论计算还确定了乙烯键在氮杂膦烷键合中的作用、transannulation 对 P-亲电试剂相互作用的影响以及静电相互作用对 transannulation 的贡献。
